WO2001003209A1 - Melange de particules de metal et/ou d'alliage et d'une substance electrolytique liquide et procede permettant de le preparer - Google Patents

Melange de particules de metal et/ou d'alliage et d'une substance electrolytique liquide et procede permettant de le preparer Download PDF

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Publication number
WO2001003209A1
WO2001003209A1 PCT/EP2000/003798 EP0003798W WO0103209A1 WO 2001003209 A1 WO2001003209 A1 WO 2001003209A1 EP 0003798 W EP0003798 W EP 0003798W WO 0103209 A1 WO0103209 A1 WO 0103209A1
Authority
WO
WIPO (PCT)
Prior art keywords
particles
alloy
metal
zinc
compact
Prior art date
Application number
PCT/EP2000/003798
Other languages
German (de)
English (en)
Inventor
Wolfgang Glaeser
Original Assignee
Grillo-Werke Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Grillo-Werke Ag filed Critical Grillo-Werke Ag
Priority to AT00927082T priority Critical patent/ATE233952T1/de
Priority to CA002378673A priority patent/CA2378673A1/fr
Priority to DK00927082T priority patent/DK1194964T3/da
Priority to US09/926,833 priority patent/US6706220B1/en
Priority to DE50001402T priority patent/DE50001402D1/de
Priority to EP00927082A priority patent/EP1194964B1/fr
Priority to JP2001508519A priority patent/JP4610146B2/ja
Priority to AU45581/00A priority patent/AU4558100A/en
Priority to SI200030045T priority patent/SI1194964T1/xx
Publication of WO2001003209A1 publication Critical patent/WO2001003209A1/fr
Priority to HK02107359.8A priority patent/HK1046063B/zh

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/244—Zinc electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a mixture of metal and / or alloy particles and a liquid electrolytic medium, and a method for producing the same.
  • Mixtures of this type are known and are used for various purposes, with particular significance being those mixtures in which the metal and / or alloy particles dissolve in the liquid electrolytic medium and can thereby give off electrical current. These are, in particular, mixtures of metal or alloy particles in which the particles can dissolve in an acid or alkali. These chemical reactions are used to a considerable extent for the production of electrical current, for example in batteries and accumulators, i.e. rechargeable batteries.
  • a very frequently used mixture consists of zinc particles or particles of a zinc alloy and solutions of alkali as a liquid electrolytic medium. These mixtures are used, for example, together with mixtures of manganese dioxide with portions of a liquid electrolytic medium, the two mixtures usually being separated from one another by a separator.
  • the particles of zinc or zinc alloys are produced from liquid zinc or liquid zinc alloys by various known methods, for example by atomizing or granulating. Depending on the process conditions, the grain sizes, the grain size distribution and the outer shapes of the particles can be set, with sieve fractions from oversize and undersize often being separated.
  • Pages 1 and 2 of this document summarize both the current state of the art and the steps taken to improve the quality.
  • the quality should be improved by using uniformly shaped zinc particles of the same size.
  • Uniform platelets are preferably used, which are mixed in more or less large amounts with other zinc powders, so that the tap density is reduced. By adding approximately 10% of such platelets, the zinc content can be reduced from 69 to 71% to 62 to 64%.
  • the object of the invention is to provide mixtures of metal and / or alloy particles and a liquid electrolytic medium which are easily reproducible, do not lead to segregation and, when installed in batteries and accumulators, have optimal properties with regard to performance and service life , Resilience due to strong discharge and mechanical shocks while avoiding the release of gases.
  • This object is now achieved in that the metal and / or alloy particles are irregularly shaped, have an uneven surface and have a bulk density below 33% by weight of the specific density of the compact metal and / or the compact alloy and the volume of the liquid Medium is larger than it corresponds to the spaces between the particles with a dry bed.
  • Such mixtures have optimal properties when the medium is solidified by a gelling agent.
  • Mixtures in which the metal and / or alloy particles consist of zinc and / or a zinc alloy are preferably used. These mixtures should preferably contain less than 65% by weight, preferably even less than 62% by weight, of zinc and / or zinc alloy.
  • Metal and / or alloy particles suitable for the mixtures according to the invention which have an uneven surface and a bulk density below 33% by weight of the specific density of the compact metal and / or the compact alloy, can be produced, for example, by a granulation process in which spicy zinc particles are formed.
  • Spratzige particles arise in particular when sudden gases escape, when metal melts and a porous cast is formed. These particles have a very broad particle size distribution, they are shaped unevenly and have an uneven surface. The surface is therefore relatively large in relation to the weight unit of the metal. The particles are nevertheless able to make a lot of direct electrical contact.
  • a gelling agent in the liquid electrolytic medium the sensitivity to mechanical impacts is significantly reduced.
  • a bulk density below 33% by weight of the specific density of the compact metal and / or the compact alloy means a bulk density of approximately 2.3 g / ml.
  • spongy granules described above it is also possible to use bulk densities below 2.3 g / ml and thus produce battery fillings with a content of less than 62% by weight of zinc mixture.
  • these mixtures have excellent properties in terms of performance, service life, resilience due to strong discharge and mechanical shocks while avoiding the release of large amounts of gases.
  • the bulk density of such metal and / or alloy particles is determined, for example, in accordance with ASTM-B 212. Such mixtures still have sufficient direct contact between almost all particles, but also have sufficient gaps for the electrolyte and the reaction products in the generation of the current.
  • the present invention thus relates not only to the mixture of metal and / or alloy particles and a liquid electrolytic medium, but also to the process for producing such a mixture, which is characterized in that the liquid metal or the liquid alloy is sprayed or granulated processed into particles which are shaped unevenly, have an uneven surface and a bulk density below 33 wt .-% of the specific gravity of the compact talls and / or the compact alloy, optionally after separation of oversize and / or undersize are introduced into a liquid electrolyte, which optionally contains a gelling agent or to which a gelling agent is added, the volume of the liquid electrolyte being greater than the gaps between corresponds to the metal or alloy particles with dry fill.
  • the invention relates to the use of unevenly shaped metal and / or alloy particles which have an uneven surface and a bulk density below 33% by weight of the specific density of the compact metal and / or the compact alloy for the production of mixtures with a liquid electrolytic medium in which the volume of the medium is greater than the spaces between the particles in the case of dry bed.
  • Figure 1 shows a previously common product with predominantly round particles and a bulk density of 3.62 g / ml.
  • FIGS. 2 to 4 show spongy products of the same zinc alloy with bulk densities of 2.40 g / ml (FIG. 2), 2.00 g / ml (FIG. 3) and 1.85 g / ml (FIG. 4).
  • FIGS. 3 and 4 show optimal results when they are processed into a mixture with a liquid electrolytic medium which contains more liquid medium than corresponds to the spaces between the particles in the case of a dry bed. Batteries made from such mixtures have optimal results in terms of performance, service life, resilience due to strong discharge and mechanical shocks while avoiding the release of gases.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Primary Cells (AREA)
  • Secondary Cells (AREA)
  • Conductive Materials (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

L'invention concerne un mélange de particules de métal et/ou d'alliage et d'une substance électrolytique liquide, qui présente comme propriété le fait que les particules de métal et/ou d'alliage sont formées irrégulièrement, qu'elles présentent une surface irrégulière et une densité en vrac inférieure à 33 % en poids de la densité spécifique du métal compact et/ou de l'alliage compact et que le volume de la substance est supérieur à celui des espaces intermédiaires entre les particules lorsque le matériau d'alimentation est sec.
PCT/EP2000/003798 1999-06-30 2000-04-27 Melange de particules de metal et/ou d'alliage et d'une substance electrolytique liquide et procede permettant de le preparer WO2001003209A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
AT00927082T ATE233952T1 (de) 1999-06-30 2000-04-27 Gemisch aus metall- und/oder legierungsteilchen und einem flüssigen elektrolytischen medium sowie verfahren zur herstellung desselben
CA002378673A CA2378673A1 (fr) 1999-06-30 2000-04-27 Melange de particules de metal et/ou d'alliage et d'une substance electrolytique liquide et procede permettant de le preparer
DK00927082T DK1194964T3 (da) 1999-06-30 2000-04-27 Blanding af metal- og/eller legeringspartikler og et flydende, elektrometrisk medium samt fremgangsmåde til fremstilling af samme
US09/926,833 US6706220B1 (en) 1999-06-30 2000-04-27 Mixture consisting of metal particles and/or alloy particles and of a liquid electrolytic medium and method for producing the same
DE50001402T DE50001402D1 (de) 1999-06-30 2000-04-27 Gemisch aus metall- und/oder legierungsteilchen und einem flüssigen elektrolytischen medium sowie verfahren zur herstellung desselben
EP00927082A EP1194964B1 (fr) 1999-06-30 2000-04-27 Melange de particules de metal et/ou d'alliage et d'une substance electrolytique liquide et procede permettant de le preparer
JP2001508519A JP4610146B2 (ja) 1999-06-30 2000-04-27 金属粒子及び／又は合金粒子と液体電解溶媒との混合物、及びそれらの製造方法
AU45581/00A AU4558100A (en) 1999-06-30 2000-04-27 Mixture consisting of metal particles and/or alloy particles and of a liquid electrolytic medium and method for producing the same
SI200030045T SI1194964T1 (en) 1999-06-30 2000-04-27 Mixture consisting of metal particles and/or alloy particles and of a liquid electrolytic medium and method for producing the same
HK02107359.8A HK1046063B (zh) 1999-06-30 2002-10-08 金屬顆粒和/或合金顆粒與液體電解介質組成的混合物及其製備方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19930214 1999-06-30
DE19930214.6 1999-06-30

Publications (1)

Publication Number Publication Date
WO2001003209A1 true WO2001003209A1 (fr) 2001-01-11

Family

ID=7913217

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/003798 WO2001003209A1 (fr) 1999-06-30 2000-04-27 Melange de particules de metal et/ou d'alliage et d'une substance electrolytique liquide et procede permettant de le preparer

Country Status (12)

Country Link
US (1) US6706220B1 (fr)
EP (1) EP1194964B1 (fr)
JP (1) JP4610146B2 (fr)
CN (1) CN1188922C (fr)
AT (1) ATE233952T1 (fr)
AU (1) AU4558100A (fr)
CA (1) CA2378673A1 (fr)
DE (1) DE50001402D1 (fr)
DK (1) DK1194964T3 (fr)
ES (1) ES2188539T3 (fr)
HK (1) HK1046063B (fr)
WO (1) WO2001003209A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1356881A1 (fr) * 2002-04-25 2003-10-29 Grillo-Werke AG Poudre de zinc ou d'alliage de zinc pour batteries alcalines
US6706220B1 (en) 1999-06-30 2004-03-16 Grillo-Werke Ag Mixture consisting of metal particles and/or alloy particles and of a liquid electrolytic medium and method for producing the same
WO2012114407A1 (fr) * 2011-02-22 2012-08-30 パナソニック株式会社 Batterie secondaire alcaline

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7045253B2 (en) * 2002-01-07 2006-05-16 Eveready Battery Company, Inc. Zinc shapes for anodes of electrochemical cells
US7413703B2 (en) * 2003-01-17 2008-08-19 Eveready Battery Company, Inc. Methods for producing agglomerates of metal powders and articles incorporating the agglomerates
US7556888B2 (en) 2004-02-13 2009-07-07 Eveready Battery Company, Inc. Electrochemical cell
US7364819B2 (en) 2004-06-28 2008-04-29 Eveready Battery Company, Inc. Alkaline electrochemical cell with a blended zinc powder
US9105923B2 (en) 2013-02-13 2015-08-11 Nanophase Technologies Corporation Zinc anode alkaline electrochemical cells containing bismuth

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3238240A1 (de) * 1982-10-15 1984-04-19 Grillo-Werke Ag, 4100 Duisburg Verfahren zur herstellung von zinkpulver fuer alkalische batterien durch verduesung
JPS59139558A (ja) * 1982-11-30 1984-08-10 Toshiba Battery Co Ltd アルカリ電池
US4606869A (en) * 1984-08-27 1986-08-19 The New Jersey Zinc Company Method of making air atomized spherical zinc powder
JPH07161356A (ja) * 1993-12-10 1995-06-23 Fuji Elelctrochem Co Ltd アルカリ電池

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4386019A (en) * 1981-07-29 1983-05-31 The United States Of America As Represented By The United States Department Of Energy Method of making electrodes for electrochemical cell
US4487651A (en) * 1983-04-06 1984-12-11 Duracell Inc. Method for making irregular shaped single crystal particles and the use thereof in anodes for electrochemical cells
JP3215446B2 (ja) * 1991-03-12 2001-10-09 三洋電機株式会社 亜鉛アルカリ電池
JPH07254406A (ja) * 1994-03-15 1995-10-03 Toshiba Battery Co Ltd 無汞化亜鉛アルカリ電池
JP3056417B2 (ja) * 1996-07-12 2000-06-26 富士電気化学株式会社 アルカリ電池用負極亜鉛基合金粉
JP2001524254A (ja) * 1997-05-02 2001-11-27 エヴァレディー バッテリー カンパニー インコーポレイテッド 電気化学電池のアノード用亜鉛形材
JPH10334908A (ja) * 1997-05-30 1998-12-18 Fuji Elelctrochem Co Ltd アルカリ電池用負極亜鉛基合金粉
WO2001003209A1 (fr) 1999-06-30 2001-01-11 Grillo-Werke Ag Melange de particules de metal et/ou d'alliage et d'une substance electrolytique liquide et procede permettant de le preparer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3238240A1 (de) * 1982-10-15 1984-04-19 Grillo-Werke Ag, 4100 Duisburg Verfahren zur herstellung von zinkpulver fuer alkalische batterien durch verduesung
JPS59139558A (ja) * 1982-11-30 1984-08-10 Toshiba Battery Co Ltd アルカリ電池
US4606869A (en) * 1984-08-27 1986-08-19 The New Jersey Zinc Company Method of making air atomized spherical zinc powder
JPH07161356A (ja) * 1993-12-10 1995-06-23 Fuji Elelctrochem Co Ltd アルカリ電池

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 008, no. 268 (E - 283) 7 December 1984 (1984-12-07) *
PATENT ABSTRACTS OF JAPAN vol. 1995, no. 09 31 October 1995 (1995-10-31) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6706220B1 (en) 1999-06-30 2004-03-16 Grillo-Werke Ag Mixture consisting of metal particles and/or alloy particles and of a liquid electrolytic medium and method for producing the same
EP1356881A1 (fr) * 2002-04-25 2003-10-29 Grillo-Werke AG Poudre de zinc ou d'alliage de zinc pour batteries alcalines
WO2003090956A1 (fr) * 2002-04-25 2003-11-06 Grillo-Werke Ag Poudre de zinc et poudre d'alliage de zinc pour piles alcalines
US7524582B2 (en) 2002-04-25 2009-04-28 Grillo-Werke Ag Zinc powder or zinc alloy powder for alkaline batteries
KR100978749B1 (ko) * 2002-04-25 2010-08-30 그릴로-베르케 아게 알칼라인 배터리를 위한 아연 분말 또는 아연합금 분말
WO2012114407A1 (fr) * 2011-02-22 2012-08-30 パナソニック株式会社 Batterie secondaire alcaline

Also Published As

Publication number Publication date
ES2188539T3 (es) 2003-07-01
CA2378673A1 (fr) 2001-01-11
EP1194964B1 (fr) 2003-03-05
CN1188922C (zh) 2005-02-09
HK1046063B (zh) 2003-07-18
JP2003504804A (ja) 2003-02-04
JP4610146B2 (ja) 2011-01-12
US6706220B1 (en) 2004-03-16
DK1194964T3 (da) 2003-06-30
AU4558100A (en) 2001-01-22
EP1194964A1 (fr) 2002-04-10
DE50001402D1 (de) 2003-04-10
ATE233952T1 (de) 2003-03-15
HK1046063A1 (en) 2002-12-20
CN1358336A (zh) 2002-07-10

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